CN1146582C - Tin catalysts, process for their prodn., their use and cross-linkable mixtures contg. same - Google Patents
Tin catalysts, process for their prodn., their use and cross-linkable mixtures contg. same Download PDFInfo
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- CN1146582C CN1146582C CNB961979429A CN96197942A CN1146582C CN 1146582 C CN1146582 C CN 1146582C CN B961979429 A CNB961979429 A CN B961979429A CN 96197942 A CN96197942 A CN 96197942A CN 1146582 C CN1146582 C CN 1146582C
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0212—Alkoxylates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0257—Phosphorus acids or phosphorus acid esters
- B01J31/0258—Phosphoric acid mono-, di- or triesters ((RO)(R'O)2P=O), i.e. R= C, R'= C, H
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/122—Metal aryl or alkyl compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/095—Compounds containing the structure P(=O)-O-acyl, P(=O)-O-heteroatom, P(=O)-O-CN
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/128—Mixtures of organometallic compounds
Abstract
The present invention relates to novel tin catalysts, a process for their production, their use and cross-linkable mixtures containing them. Storage-stable crosslinkable RTV-1 compositions comprising at least one tin catalyst obtained by the reaction of at least one organotin compound with at least one monoorthophosphoric acid or mixture of mono and di-orthophosphoric acids, and at least one crosslinkable polysiloxane.
Description
The present invention relates to novel tin catalyst, its production method and application, and the crosslinking mixture that contains these novel tin catalysts.
Generally all know the catalyst applications of organo-tin compound as crosslinked condensation 1 and 2 composition polysiloxane compositions, after this all claim this composition be RTV-1 and RTV-2 (this two abbreviation converges first letter by following predicate and constitutes:
rOom
tEmperature
vUlcansing component
1Or
2(self cure composition 1 or 2)), this composition produces elastomerics by the effect of water or the moisture-curing that absorbs in the atmosphere.
Two organic group tin compounds all are the catalyzer that is commonly used to as polysiloxane composition such as the reaction product of dialkyltin dicarboxylates or itself and alcoxyl silane.For example, such compound is the reaction product of dibutyltin diacetate, two sad dibutyl tins, dibutyl tin laurate, two sad dioctyl tins, two lauric acid dioctyl tins or dibutyltin oxide and silicon ester especially, such as the many methyl ester of silicic acid, silicic acid tetrem oxygen ester and the many ethyl esters of silicic acid.
U.S. Pat-A3,525,778 other records have inferior stannic acid organophosphate, its general formula:
R
4-m-nSn(Y
m)[OP(O)(OR’)
2]
n
Wherein
Y refers to halogen, alkoxyl group or aryloxy group;
R and R ' are meant the optional hydrocarbyl group that replaces;
M is 0,1 or 2; N is 1,2 or 3; The m+n sum is 1,2 or 3, has has also recorded and narrated them as the Application of Catalyst of solidifying polysiloxane composition.These products are distinguished by the result of activity rising and fast setting polysiloxane composition.
But, when using polysiloxane composition, condensation reaction is had the shortcoming that the ideal catalytic activity also produces unfavorable polymer degradation reaction though the tin catalyst known to the document shows them.So just cause the bridging property loss of energy of RTV-1 product for example or weaken.Also may occur the reaction of polymer degradation in the RTV-2 product, wherein catalyzer normally stores with single component and only mixed in short time with other composition before using this product.Consequently especially in storage the composition of catalyzer degraded, particularly formulation in the pasty state and viscosity descend or its reactive behavior changes unfriendly.
The object of the present invention is to provide the tin catalyst that does not possess the known product shortcoming and be applicable to catalyzer as RTV-1 and RTV-2.
Be surprisingly found out that now the reaction product of organo-tin compound and ortho-phosphoric acid and/or its ester all has the advantage that obviously is better than the document known compound.Be specially adapted to the catalyzer of conduct condensation cross-linking polysiloxane composition in the RTV product that the production stability in storage is obviously improved according to this novel tin catalyst of the present invention.And this novel tin catalyst most characteristic be that its reactive behavior improves.
Therefore the invention provides by the obtainable novel tin catalyst of the reaction of following component:
A), at least a organo-tin compound with
B), at least a single ortho-phosphoric acid ester and/or ortho-phosphoric acid and
C), optional other phosphoric acid ester,
D), choose any one kind of them organoalkoxysilane or two or more organoalkoxysilane.
The term organo-tin compound a) comprises any prior art compound known.
Preferably have machine tin compound and a) be single, double and three organic group tin compounds, its general formula is:
R
1 4-nSnX
n (I)
Wherein n=1,2 or 3 is preferably n=2.
R
1The C of=straight or branched
1~C
30Alkyl, C
5~C
14Cycloalkyl or C
6~C
14Aromatic yl group and
The X=halogen ,-OR
1,-OC (O) R
1-OH ,-SR
1,-NR
1 2,-NHR
1,-OSiR
1 3,-OSi (OR)
1 3And/or general formula is R
1 2SnX ', R
1 3SnX '
1/2And/or R
1SnX '
3/2, wherein X '=O, S.
Here, the C of straight or branched
1~C
30Alkyl, C
5~C
14Cycloalkyl or C
6~C
14Hydrogen atom on the aromatic yl group can be by halogen atom, OH, NH
2, NO
2Or C
1-C
6Alkyl group replace.
Even these radicals X, X ' and R
1More than occurring once in molecule, they are all identical or different.
Particularly preferred compound is di-n-octyltin oxide, dibutyltin oxide, dichloride tin methide, dichloride dibutyl tin, monochlor(in)ate tributyl tin, dibutyl tin laurate, dibutyltin diacetate, toxilic acid dibutyl tin, two caproic acid dibutyl tins, two sad dibutyl tins, two sad dioctyl tins, two lauric acid dioctyl tins, inferior stannic acid dioctyl dibutoxy ester and/or inferior stannic acid tributyl ethoxylated ester.
For purpose of the present invention, single ortho-phosphoric acid ester and/or ortho-phosphoric acid b) preferably include ortho-phosphoric acid and/or its ester with following general formula:
O=P(OR
2)
3-m(OR
3)
m (II)
Here, m=2 or 3 is preferably 2.
R
2The C of=straight or branched
1~C
30Alkyl, acyl group, C
2~C
30Alkane thiazolinyl or alkoxyalkyl, C
5~C
14Cycloalkyl or C
6~C
14Aromatic yl group, or three organic group silyls or two organic group alkoxysilyl groups;
R
3=hydrogen and/or a kind of metal are preferably a kind of alkali or alkaline-earth metal;
And/or compound with general formula III:
[O=P(OR
2)
c(OR
3)
bO
a]
a-a·[NH
xR
5 4-x]
+ (III)
Can be made as 1 to 3 with x, comprise 3 numerical value;
R
5=C
1~C
30Alkyl and (CH
2)
zSi (OR
6)
3
Wherein z=1~10 are preferably 3, a+b+c=3 here, wherein
It is 1 to 3 numerical value that a can be made as, and comprises 3
It is 0 to 2 numerical value that b can be made as, and comprises 2
It is 0 to 2 numerical value that c can be made as, and comprises 2
R
6=C
1~C
5Alkyl, C
2~C
6Alkyl alkoxy and/or polyphosphate.
In one group of preferred embodiment of the present invention, the compound of this general formula III is:
Here, the C of straight or branched
1~C
30Alkyl, acyl group, C
2~C
30Alkane thiazolinyl or alkoxyalkyl, C
5~C
14Cycloalkyl or C
6~C
14Hydrogen atom on the aromatic yl group also can be by for example halogen formerly give, OH, NH
2, NO
2Or other C
1~C
6Alkyl group replaces.
In one group of preferred embodiment of the present invention, single ortho-phosphoric acid ester contains the C of at least a linearity or branched chain
4~C
30Alkyl group such as R
2The example of preferred ester class is mono phosphoric acid ester butyl ester, mono phosphoric acid ester isodecyl ester, mono phosphoric acid ester-(2-ethylhexyl) ester, mono phosphoric acid ester decyl ester, mono phosphoric acid ester polyhexamethylene, mono phosphoric acid ester tridecyl ester and/or mono phosphoric acid ester stearyl.Since the result of this production method, single ortho-phosphoric acid ester b) can comprise dibasic acid esters, Tripyrophosphoric acid and/or ortho-phosphoric ester as impurity.Independent ortho-phosphoric acid is not too preferred, and preferably uses a kind of and mixture its ester class.
Under the situation of preferred n=2, preferably include the unit or the compound of following structure according to this tin catalyst of the present invention:
-R
1 2Sn-O-P(O)(OR
2)-O-Sn(R
1 2)-,
And/or
For purpose of the present invention, phosphoric acid ester c) the preferably dibasic acid esters and three esters of ortho-phosphoric acid and/or Tripyrophosphoric acid.
Preferred phosphoric acid ester c) embodiment is ortho-phosphoric dibasic ester or ternary ester, such as di(2-ethylhexyl)phosphate butyl ester, di(2-ethylhexyl)phosphate-(2-ethylhexyl) ester, the two hexadecyl esters of phosphoric acid, phosphoric acid diisononyl esters, two (trimethyl silyl) esters of phosphoric acid, tricresyl phosphate butyl ester, tricresyl phosphate-(2-ethylhexyl) ester, tricresyl phosphate (hexadecyl) ester, tricresyl phosphate and nonyl ester and/or tricresyl phosphate (trimethyl silyl) ester.
Composition c) also comprise the polyphosphate class, or the mixture of two or more polyphosphate and/or ortho-phosphoric acid ester.The acidity of ortho-phosphoric acid or polyphosphate or neutral salt such as an alkali metal salt, also all suit.
For purpose of the present invention, organoalkoxysilane d) silicon ester preferably, such as poly-methyl silicate, TSL 8114, ethyl polysilicate, silicic acid tetraethyl ester, silicic acid tetrapropyl ester, organic group trialkoxy silane, such as vinyl trimethoxy silane, vinyltriethoxysilane, Union carbide A-162, methyltrimethoxy silane, vinyl tripropoxy silane, vinyltriethoxysilane or its partial hydrolysate.
Methyl trimethoxy oxygen base, methyl triethoxy, ethene Trimethoxy silane and/or vinyl triethoxysilane all are particularly preferred in this respect.
In addition, can comprise the other auxiliary substance according to this mixture of the present invention.
These auxiliary substances are organic solvent preferably, such as toluene, hexane, isomery paraffinic hydrocarbon, tinting pigment and/or organic acid such as 2 ethyl hexanoic acid, phenylformic acid, Witco 1298 Soft Acid.
For purpose of the present invention, preferred tin catalyst is can be by following:
1 mole of at least a organo-tin compound a), especially preferably a kind of binary organo-tin compound;
0.5~4 moles, preferably 1~3 mole particularly preferably is 1.5~2.5 moles at least a single ortho-phosphoric acid ester and/or ortho-phosphoric acid b), preferably single ortho-phosphoric acid;
0~2 mole, 0 mole two and/or three ortho-phosphoric acid ester c preferably) and
0~5 mole at least a organoalkoxysilane d) reaction obtains.
Tin catalyst very particularly preferably is by following:
1 mole of at least a binary organo-tin compound a) with
1~3 mole of at least a single ortho-phosphoric acid ester and
The reaction of 0~5 mole of at least a organoalkoxysilane is available.
According to this tin catalyst of the present invention preferably, by using suitable tin compound and phosphorus compound between 20~200 ℃, preferably between 20~140 ℃, react available.In another research of the present invention, this reaction is preferably carried out in suitable organic solvent.Any inert solvent all is applicable to this purpose, such as arene such as benzene,toluene,xylene and fat hydrocarbon and optional halogenated hydro carbons, such as hexane, heptane and tetrachloromethane.Wherein, this reaction is carried out between 20~200 ℃ temperature usually, if wherein adopted solvent, then temperature of reaction also will be determined according to the boiling point of solvent.
In another group preferred embodiment, this tin catalyst is can be by making at least a organo-tin compound a), at least a single ortho-phosphoric acid ester and/or ortho-phosphoric acid b), also optional other phosphoric acid ester c) and choose any one kind of them or several organoalkoxysilanes d) under the temperature between 20~140 ℃, react and obtain.
The present invention also provides a kind of method of producing this tin catalyst according to the present invention, it is characterized in that:
A), at least a organo-tin compound with
B), at least a single ortho-phosphoric acid ester and/or ortho-phosphoric acid and
C), optional other phosphoric acid ester and
D), choose any one kind of them or several organoalkoxysilanes.
In the process of reacting according to the present invention, some auxiliary substances in addition, such as organic solvent such as toluene, hexane, isomery paraffinic hydrocarbon, tinting pigment, and/or organic acid such as 2 ethyl hexanoic acid, phenylformic acid, Witco 1298 Soft Acid also can exist.
This reaction is preferably carried out under the temperature between 20~200 ℃, is preferably the temperature between 20~140 ℃.
The present invention also provides according to tin catalyst of the present invention as the catalyzer in polyolefine, polyester, oil, lipid acid, urethane and polysiloxane and the application of stablizer.It is this according to the catalyzer of tin catalyst of the present invention as crosslinkable RTV-1 and RTV-2 composition particularly preferably to be application.
In the time of in the product that will be applied to RTV-2 according to catalyzer of the present invention, it is favourable for adopting silicon-dioxide, paraffinic hydrocarbon, Vaseline or the paraffin of filler such as high dispersive in order to obtain a kind of paste-like appearance.The quantity of auxiliary substance, with respect to all compositions a) to d) for be very relevant with the character and the concentration thereof of used composition, also the stickiness with required paste-like preparation is very relevant.
The present invention also further provides and has comprised:
At least a according to tin catalyst of the present invention
At least a crosslinkable polysiloxane,
Choose any one kind of them or several silane crosslinkers,
Optional filler reaches
The optional other additive and the crosslinkable RTV composition of auxiliary substance.
According to this RTV composition of the present invention can be that 1-or 2-become sub-system in this case.Become in the sub-system at 1-, all compositions all are mixed.The system of 2-composition then adopts two kinds of separate constituents to produce, and just remix is together before just using.Here, this crosslinkable silicone is to store so that a kind of mode of composition is independent traditionally, and silane crosslinker and catalyzer store in other mode.
According to the quantity of this tin catalyst of the present invention 0.005~5wt.% preferably, be preferably 0.01~2.0wt.%, be preferably 0.1~1wt.% especially, with respect to the total amount of all the components.
For purpose of the present invention, crosslinkable polysiloxane is poly-two organic group siloxanes, is preferably polydimethylsiloxane, and wherein methyl group is can choose wantonly with vinyl, phenyl, C
2~C
8Alkyl or alkylhalide group group partly replace.Polydimethylsiloxane preferably mainly is linear, but also can exist small part that the organosiloxy unit of crosslinked action is arranged.The viscosity of this polymkeric substance is preferably 0.1~4000Pas, especially is preferably 5~1000Pas.Crosslinkable poly-two organic group siloxanes can partly be replaced such as the trimethylsiloxane group group with the anergy group in addition.
The group that preferably has reactive behavior of polysiloxane is OH group or tri-alkoxy methyl-monosilane base or dialkoxy methyl-monosilane base group in the RTV-1 composition.Preferred tri-alkoxy methyl-monosilane base or dialkoxy methyl-monosilane base group are triethoxy methyl silicane base and trimethoxymethylsila,e base, diethoxymethyl methyl-monosilane base, diethoxy vinyl methyl-monosilane base, dimethoxy-methyl methyl-monosilane base and dimethoxy vinyl methyl-monosilane base group.
In one group of preferred embodiment of the present invention, this has with tri-alkoxy methyl-monosilane base or dialkoxy methyl-monosilane base group is (the consulting for example DE-A 4 207212) of adopting proper method to produce in the process of producing the RTV product as the crosslinkable polysiloxane of the active group that responds.
The group of this reactive behavior of polysiloxane OH group preferably in the RTV-2 composition.
For purpose of the present invention, silane crosslinker is the known silane of any prior art, promptly has the silane of acetoxyl group, alkoxyl group, alkoxyalkoxy group, azyloxy, amino, amido, kharophen and oximido.The example of these linking agents is; Methyl triacetoxysilane, ethyl triacetoxysilane, methyltrimethoxy silane, Union carbide A-162, silicic acid tetraethyl ester, vinyltriethoxysilane, vinyltrimethoxy silane, silicic acid tetrapropyl ester, methyl three-(methyl ethyl ketone oxime) silane, methyl ethoxy two-N-toluyl aminosilane, methyl three-(butyl amino) silane and methyl three-(diethyl aminooxy) silane.
Silane crosslinker is preferably at least a organoalkoxysilane in the RTV-2 composition, such as methyltrimethoxy silane, silicic acid tetraethyl ester, vinyltriethoxysilane, vinyltrimethoxy silane, silicic acid tetrapropyl ester and/or its partial hydrolysate.
Filler is preferably and strengthens or enhanced filler not, such as the system of forging or deposition of silica, carbon black, SiO 2 powder.It is through surface modification that this kind filler also can be chosen wantonly.The mixture of the filler of any desired composition also can use.In one group of preferred embodiment of the present invention, this filler is a silicon-dioxide.
Be preferably softening agent, coupling agent, pigment, stablizer, other promotor and sterilant for the object of the invention additive.
In one group of preferred embodiment of the present invention, auxiliary substance is the siloxanes softening agent, such as have a trimethylsiloxy group end group with viscosity be the polydimethylsiloxane of 0.1~5Pas; Stablizer, such as hexamethyldisilazane and/or at U.S. Pat-A4, cited compound in 417,042; Coupling agent, such as the silane of organo-functional group with general formula (IV):
Z-CH
2-CH
2-CH
2-Si(OR
4)
3-dR
4 d (IV)
D=0 or 1 wherein,
-O-C (O)-C (CH
3)=CH
2,-SH ,-OH ,-Cl ,-CN and
R
4The C of=straight or branched
1~C
30Alkyl group and general formula be the group of (V):
Or urea derivative.
At R
4In the hydrogen atom here can partly use halogen atom, OH, NH
2, NO
2Or also can use additional C
1~C
6Alkyl group replaces.
In one group of preferred embodiment of the present invention, this produces by original position in cross-linkable composition RTV according to tin catalyst of the present invention.
Therefore, the invention provides and comprise at least a tin catalyst, at least a crosslinkable polysiloxane, choose any one kind of them or the RTV composition of the crosslinked mistake of several silane crosslinkers and optional other additive and auxiliary substance, it is characterized in that, this tin catalyst is that original position is passed through at least a organic group tin compound a) when producing crosslinkable RTV composition, at least a single ortho-phosphoric acid ester and/or ortho-phosphoric acid b) and optional other phosphoric acid ester c), a kind of or several organoalkoxysilanes d) and/or other auxiliary substance e) reaction produce.
The organo-tin compound here is preferably the reaction product of a kind of oxidation two organic group tin and silicon ester and/or carboxylic acid two organic group tin, such as dibutyltin oxide and di-n-octyltin oxide, dibutyltin diacetate and two sad dioctyl tins, with components b) be preferably at least a ortho-phosphoric acid monoesters such as mono phosphoric acid ester butyl ester, mono phosphoric acid ester isodecyl ester, mono phosphoric acid ester-(2-ethylhexyl) ester, mono phosphoric acid ester decyl ester, mono phosphoric acid ester polyhexamethylene, mono phosphoric acid ester tridecyl ester and mono phosphoric acid ester stearyl.Particularly preferably be mono phosphoric acid ester isodecyl ester, mono phosphoric acid ester-(2-ethylhexyl) ester, mono phosphoric acid ester decyl ester, the basic ester of mono phosphoric acid ester, mono phosphoric acid ester tridecyl ester and mono phosphoric acid ester stearyl.
In one group of preferred embodiment of the present invention, crosslinkable RTV composition is the composition of following component:
At least a crosslinkable polysiloxane of 100 parts of weights;
0.5 at least a silane crosslinker of~20 parts of weights;
0.005~5 parts of weights is at least a according to tin catalyst of the present invention;
At least a filler of 0~500 part of weight and
The other additive and the auxiliary substance of 0~200 part of weight.
Here the preferably following composition of additive and auxiliary substance:
The softening agent of 0~100 part of weight;
The coupling agent of 0~20 part of weight;
The pigment of 0~100 part of weight;
The sterilant of 0~20 part of weight and
The promotor of 0~20 part of weight and stablizer reach
The scavenging agent of 0~5 part of weight.
Wherein the total amount of additive of all in mixture and auxiliary substance is greater than 0 with mostly be 200 parts of weights most.
Each composition of this crosslinkable RTV composition can be mixed by any desired sequence.It is preferred at room temperature mixing these compositions.According to this tin catalyst of produced in situ of the present invention the time, each composition preferably at room temperature stirs together.
This RTV composition can be produced in the mixing device of any traditional prior art, such as planetary stirrer, high-speed mixer, butterfly type mixing tank or the screw of operation batching continuously.
Following embodiment is to explanation of the present invention and unrestricted.
Embodiment
Embodiment 1
Mono phosphoric acid ester-2-the (ethyl hexyl) ester of 150 gram di-n-octyltin oxides and 87.2 grams is introduced under nitrogen protection in the gram of 400 in the there-necked flask that is contained in belt stirrer, thermometer, reflux exchanger and the water trap toluene.Slow this mixture to 125 of heating ℃ and stirring simultaneously, the water that reaction generates is with toluene formation azeotropic mixture and steamed, and separates through water trap again.After about 3 hours, reaction is finished, and does not have again water to steam.Again this reaction mixture is evaporated under 50 millibars in 80~100 ℃ and vacuum, to residue toluene level 17wt%.Promptly obtain a kind of light yellow transparent liquid.According to ultimate analysis, this product tin content reaches 17.8%.
Embodiment 2
Mono phosphoric acid ester-2-the (ethyl hexyl) ester of 150 gram di-n-octyltin oxides, 174 grams and the silicic acid tetrapropyl ester of 178.7 grams are introduced in the there-necked flask that is connected with agitator, thermometer, reflux exchanger under nitrogen protection.Slowly this mixture to 160 of heating ℃ stirs simultaneously, again stir about 3 hours under this temperature.Again this mixture is cooled off, replace this reflux exchanger, and under standard atmosphere pressure and 160 ℃, steam all volatile constituents within an hour with the water distilling apparatus that has a condenser.Isolate overhead product 73.3 grams, be accredited as propyl alcohol through gas chromatographic analysis.Reaction product is a yellow transparent liquid, and its tin content is 11.2% (group is according to ultimate analysis).
Embodiment 3
Di(2-ethylhexyl)phosphate-2-the (ethyl hexyl) ester of 200 gram di-n-octyltin oxides, 178.3 grams and the phosphoric acid of 64 grams 85% are introduced in the there-necked flask that is connected with agitator, thermometer, reflux exchanger and water trap under nitrogen protection.Under agitation slowly heat this mixture to 120 ℃, water generation reaction and toluene constitute azeotropic mixture and are steamed, and are separated in water trap.After about 2 hours, reaction is finished, and no longer includes water and steams.Reaching the initial stage down in 110 ℃ of maximum temperatures again is that standard pressure then is to evaporate this reaction mixture under 5 millibars of vacuum to the about 10wt% of residue toluene amount.What obtain is a kind of light yellow transparent liquid.Reach 14.4% according to this product tin content of ultimate analysis.
Reference examples 4
The silicic acid tetrapropyl ester of getting 1368 gram di-n-octyltin oxides and 1632 grams is introduced in the there-necked flask that is connected with agitator, thermometer, reflux exchanger under nitrogen protection.Slowly this mixture to 160 of heating ℃ stirs simultaneously, more about 5 hours of restir under this temperature.What obtain is a kind of light yellow transparent liquid.Reach 14.5% according to this product tin content of ultimate analysis.
Embodiment 5
Getting product 70 grams that produce among the embodiment 4 at room temperature reacts with 37 gram mono phosphoric acid ester-2-(ethyl hexyl) esters.This mixture is a clear, colorless liquid, the RTV-1 composition that is used for after this testing.
Embodiment 6
Di(2-ethylhexyl)phosphate-2-the (ethyl hexyl) ester of 100 gram dibutyltin oxides and 168.7 grams is introduced under nitrogen protection in the gram of 300 in the there-necked flask that is contained in belt stirrer, thermometer, reflux exchanger and the water trap toluene.Slowly this mixture to 125 of heating ℃ stirs simultaneously, and within about 3 hours, the water that reaction generates is with toluene formation azeotropic mixture and steamed, and is separated in water trap.This reaction mixture of evaporation under 110 ℃ and 10 millibars of vacuum again is to residue toluene level 11wt%.What obtain is a kind of light yellow transparent liquid.Reach 15.4% according to this product tin content of ultimate analysis.
Reference examples 7
Prepare a kind of toluene and account for 50% two sad dibutyl tin solution.This tin catalyst is used to contrast purpose, is a kind of known product, and uses as a kind of catalyzer in prior art.
Produce and estimate the general procedure of RTV-1 composition
In 1 liter planet amalgamator according to following embodiment production said composition.After finishing production, said composition to be delivered in the plastic socket, the material of next step test is exactly to take out in the sleeve that from then on seals.
The cross-linking properties test of polysiloxane composition is carried out on a glass sheets, thick this mashed prod to 2mm of coating on the 40 * 60mm area of a side of this sheet glass.After 24 hours, check this material, determine its whether completely solidified on the surface of this glass.
The mechanical property of vulcanized rubber is thick in 2mm by this mashed prod is cut into slices, and is cured under 23 ℃ and 50% relative humidity, press the method for DIN 53 504 its performances of detection after 14 days again and is determined.Its hardness detected according to the method for DIN 53 505 after 21 days.
The stability in storage of product adopts the method that this mashed prod is stored in the sealed tube under the temperature of 50 ℃ or 100 ℃ to be estimated.To the sample that stores down at 50 ℃, the sample of pipe taking-up from then on once carries out crosslinked detection weekly.If sample is crosslinked fully after the week, can think that then this is up to the standards.For the sample that is stored under 100 ℃, then take out material sample every day and detect.If this sample is promptly crosslinked fully after 1 day, think that then this is up to the standards.The detection of carrying out stability in storage under 50 ℃ and 100 ℃ belongs to a kind of seal gum test method of routine, in fact allows the evaluation of the stability in storage of product is carried out in relatively than short duration.
Embodiment 8 to 13
That gets 55.0 parts of weights has a Si (CH=CH
2) (OCH
3)
2When the polydimethylsiloxane of end group, 25 ℃ of its viscositys is 80Pas, with having-OSi (CH of 29.0 parts of weights
3)
3The polydimethylsiloxane of end group, its 25 ℃ of viscositys are 100mPas, mix mutually in the planet blunger with the vinyltrimethoxy silane of 2.5 parts of weights.The water drain silica that adds 9.5 parts of weights again in this mixture, the commodity Aerosil R 972 by name that obtains from Degussa company and mix this mixture and then obtain a kind of even mashed prod.The 3-aminopropyltriethoxywerene werene that adds 0.8 part of weight again and is finished test by adding as the tin catalyst of institute's number of columns in the table 1 in this mixture.
The RTV-1 product of embodiment 8 to 13 completion of cure all after producing.Can find out detected result from table 1.Embodiment 13 explanation according to tin catalyst of the present invention can be in the production process of seal gum produced in situ.
Embodiment 14 to 19
That gets 55.0 parts of weights has a Si (CH=CH
2) (OCH
3)
2The polydimethylsiloxane of end group, be 80Pas during 25 ℃ of its viscositys, with having-OSi (CH of 29.0 parts of weights
3)
3The polydimethylsiloxane of end group, its 25 ℃ of viscositys are 100mPas, mix mutually in the planet blunger with the vinyltrimethoxy silane of 2.5 parts of weights.The water drain silica that adds 9.5 parts of weights in this mixture again, the commodity Aerosil R 972 by name that obtains from Degussa company, and be in harmonious proportion this mixture and then obtain a kind of even mashed prod.Add 0.8 fen heavy 3-aminopropyltriethoxywerene werene again in this mixture, and the hexamethyldisilazane by adding quantity described in table 2 and the tin catalyst of institute's number of columns wherein, test promptly finished.
The equal completely solidified of RTV-1 product after producing.Test-results sees Table 2.Embodiment 17 to 19 shows, because the amount of stablizer hexamethyldisilazane increases (0.4 part of weight, embodiment 18, see Table 2), can be observed stability in storage and improves significantly.Comparing with traditional tin catalyst (controlled trial 15,16), is better significantly according to catalyzer of the present invention and hexamethyldisilazane bonded stability in storage.
The result of table 1 embodiment 8 to 13
Embodiment No | Tin catalyst | Parts by weight | Hardness [Shore A] DIN53505 | Fracture extensibility [%] DIN53504 | Tensile stress (100% stretches) [MPa] DIN53504 | Tear strength [MPa] DIN53504 | 50 ℃ of stability in storagies [week] | 100 ℃ of stability in storagies [my god] |
8 1) | Embodiment 4 | 0.4 | 19 | 550 | 0.30 | 1.01 | 0 | 0 |
9 1) | Embodiment 7 | 0.4 | 20 | 405 | 0.42 | 1.29 | 4 | 3 |
10 | Embodiment 2 | 0.52 | 23 | 495 | 0.41 | 1.52 | 14 | 12 |
11 | Embodiment 5 | 0.61 | 23 | 560 | 0.38 | 1.60 | 20 | 15 |
12 | Embodiment 6 | 0.34 | 22 | n.d | - | - | 18 | 13 |
13 2) | Embodiment 4 | 0.6 | 21 | 490 | 0.39 | 1.41 | 22 | 11 |
Annotate
1): reference examples
Annotate
2): the mono phosphoric acid ester-2-(ethyl hexyl) ester that adds other 0.32 part of weight in this batch of material
Annotate
3): the mono phosphoric acid ester-2-(ethyl hexyl) ester that adds other 0.36 part of weight in this batch of material
N.d: undetermined
The result of table 2 embodiment 14 to 19
Embodiment No | Tin catalyst | Parts by weight | Hexamethyl two single silane [parts by weight] | Hardness [Shore A] DIN53505 | Fracture extensibility [%] DIN53504 | Tensile stress (100% stretches) [MPa] DIN53504 | Tear strength [MPa] DIN53504 | 100 ℃ of stability in storagies [my god] |
14 1) | Embodiment 4 | 0.4 | 1.0 | 20 | 590 | 0.20 | 0.64 | 2 |
15 1) | Embodiment 7 | 0.4 | 1.0 | 20 | 490 | 0.43 | 1.50 | 11 |
16 | Embodiment 5 | 0.61 | 1.0 | 20 | 475 | 0.36 | 1.27 | 25 4) |
17 | Embodiment 5 | 0.60 | 0.8 | 19 | 460 | 0.38 | 1.30 | 25 |
18 | Embodiment 5 | 0.60 | 0.4 | 21 | 500 | 0.38 | 1.40 | 22 |
19 | Embodiment 5 | 0.60 | 0.2 | 21 | 490 | 0.38 | 1.40 | 12 |
Annotate
1): reference examples
Annotate
4): exceed described period, this product remains crosslinkable; Test does not continue.
Claims (13)
1, the tin catalyst that is made by following reaction is as the Application of Catalyst of condensation crosslinkable silicone compositions:
A) at least a organo-tin compound with
B) ester of at least a single ortho-phosphoric acid ester, ortho-phosphoric acid, formula (11)
O=P(OR
2)
3-m(OR
3)
m (II)
M=2 or 3 wherein;
R
2The C of=straight or branched
1~C
30Alkyl, acyl group, C
2~C
30Alkenyl or alkoxyalkyl, C
5~C
14Cycloalkyl or C
6~C
14Aromatic yl group, or three organic group silyls or two organic group alkoxysilyl groups;
R
3=a kind of metal, or
The compound of formula III
[O=P(OR
2)
c(OR
3)
bO
a]
a-a·[NH
xR
5 4-x]
+ (III)
Wherein x is 1 to 3;
R
5=C
1~C
30Alkyl or (CH
2)
zSi (OR
6)
3
Z=1-10 wherein, a+b+c=3, wherein
A is 1 to 3,
B is 0 to 2,
C is 0 to 2;
R
6=C
1~C
5Alkyl, C
2~C
6Alkyl alkoxy or polyphosphate;
C) non-essential other phosphoric acid ester reaches
D) non-essential a kind of organoalkoxysilane or two or more organoalkoxysilane react.
2, according to the application of claim 1, wherein organo-tin compound is formula (I) compound:
R
1 4-nSnX
n (I)
N=1,2 or 3 wherein,
R
1The C of=straight or branched
1~C
30Alkyl, C
5~C
14Cycloalkyl or C
6~C
14Aromatic yl group and
The X=halogen ,-OR
1,-OC (O) R
1,-OH ,-SR
1,-NR
1 2,-NHR
1,-OSiR
1 3,-OSi (OR
1)
3Or general formula is R
1 2SnX ', R
1 3SnX '
1/2Or R
1SnX '
3/2Compound, wherein X '=O, S.
3, according to the application of claim 1, wherein single ortho-phosphoric acid ester or ortho-phosphoric acid are a kind of following formula: compounds:
O=P(OR
2)
3-m(OR
3)
m (II’)
M=2 or 3 wherein;
R
2The C of=straight or branched
1~C
30Alkyl, acyl group, C
2~C
30Alkenyl or alkoxyalkyl, C
5~C
14Cycloalkyl or C
6~C
14Aromatic yl group, or three organic group silyls or two organic group alkoxysilyl groups;
R
3=hydrogen or a kind of metal,
Or formula III compound:
[O=P(OR
2)
c(OR
3)
bO
a]
a-a·[NH
xR
5 4-x]
+ (III)
With x be 1 to 3;
R
5=C
1~C
30Alkyl or (CH
2)
zSi (OR
6)
3
Z=1-10 wherein, a+b+c=3, wherein
A is 1 to 3,
B is 0 to 2,
C is 0 to 2;
R
6=C
1~C
5Alkyl, C
2~C
6Alkyl alkoxy or polyphosphate.
4, according to the application of claim 1, amount of component b wherein) be the dibasic ester and the ternary ester of ortho-phosphoric acid or Tripyrophosphoric acid.
5, according to the application of claim 1, component d wherein) comprise silicon ester, organic group trialkoxy silane or its partial hydrolysate.
6, according to the application of claim 1, wherein tin catalyst also comprises organic solvent, tinting pigment or organic acid as auxiliary substance e).
7, according to the application of claim 1, wherein tin catalyst a) obtains with 1~3 mole of at least a single ortho-phosphoric acid ester and 0~5 mole of at least a organoalkoxysilane reaction by 1 mole of at least a two organic group tin compound.
8, crosslinkable RTV polysiloxane composition comprises
0.005-5 the tin catalyst of definition at least a claim 1 of weight part,
At least a crosslinkable polysiloxane of 100 weight parts,
0.5-20 non-essential a kind of or several silane crosslinkers of weight part,
The non-essential filler of 0-500 weight part reaches
The non-essential other additive and the auxiliary substance of 0-200 weight part.
9, according to the crosslinkable RTV polysiloxane composition of claim 8, wherein silane crosslinker be methyl trimethoxy oxygen base-, methyl triethoxy, vinyl trimethoxy or vinyltriethoxysilane.
10, a kind of crosslinkable RTV polysiloxane composition, it comprises:
0.005-5 at least a tin catalyst of weight part,
At least a crosslinkable polysiloxane of 100 weight parts,
0.5-20 non-essential a kind of or several silane crosslinkers of weight part and
The non-essential other additive or the auxiliary substance of 0-500 weight part,
Wherein tin catalyst be make following material react with the process of producing crosslinkable RTV composition in produced in situ:
1 mole of at least a organo-tin compound a),
0.5-4 at least a single ortho-phosphoric acid ester of mole or ortho-phosphoric acid b),
The non-essential other phosphoric acid ester c of 0-2 mole),
A kind of or several organoalkoxysilanes d of 0-5 mole) and
Auxiliary substance e in addition),
Or their combination.
11,, it is characterized in that it also comprises silicon-dioxide according to the crosslinkable RTV polysiloxane composition of claim 10.
12, according to the crosslinkable RTV polysiloxane composition of claim 10, it is characterized in that single ortho-phosphoric acid ester b) be mono phosphoric acid ester isodecyl ester, mono phosphoric acid ester-(2-ethylhexyl) ester, mono phosphoric acid ester decyl ester, mono phosphoric acid ester polyhexamethylene, mono phosphoric acid ester tridecyl ester or mono phosphoric acid ester stearyl.
13, according to the application of claim 1, wherein tin catalyst is as the catalyzer of RTV-1 or RTV-2 component polysiloxane composition.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19533963.0 | 1995-09-13 | ||
DE1995133963 DE19533963C1 (en) | 1995-09-13 | 1995-09-13 | Phosphorus-contg. organo-tin catalysts for silicone materials |
Publications (2)
Publication Number | Publication Date |
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CN1200738A CN1200738A (en) | 1998-12-02 |
CN1146582C true CN1146582C (en) | 2004-04-21 |
Family
ID=7772077
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB961979429A Expired - Lifetime CN1146582C (en) | 1995-09-13 | 1996-09-02 | Tin catalysts, process for their prodn., their use and cross-linkable mixtures contg. same |
Country Status (15)
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---|---|
US (1) | US6162756A (en) |
EP (1) | EP0850254B1 (en) |
JP (1) | JP4157162B2 (en) |
CN (1) | CN1146582C (en) |
AT (1) | ATE224920T1 (en) |
AU (1) | AU711271B2 (en) |
CA (1) | CA2231586C (en) |
CZ (1) | CZ289135B6 (en) |
DE (2) | DE19549425A1 (en) |
ES (1) | ES2184888T3 (en) |
HU (1) | HU224309B1 (en) |
NZ (1) | NZ318387A (en) |
PL (1) | PL186608B1 (en) |
WO (1) | WO1997010271A1 (en) |
ZA (1) | ZA967686B (en) |
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DE10151477A1 (en) | 2001-10-18 | 2003-05-15 | Wacker Chemie Gmbh | Crosslinkable compositions based on organosilicon compounds |
DE10158520A1 (en) * | 2001-11-29 | 2003-06-26 | Wacker Chemie Gmbh | Masses which can be crosslinked by splitting off alcohols from alkoxysilyl end groups to give elastomers |
WO2003051124A2 (en) * | 2001-12-18 | 2003-06-26 | Henkel Kommanditgesellschaft Auf Aktien | Inhibition of the asexual reproduction of fungi |
DE10218490B4 (en) * | 2002-04-25 | 2007-09-13 | Wacker Chemie Ag | With elimination of alcohols from alkoxysilyl end groups to elastomers crosslinkable compositions |
US20040225079A1 (en) * | 2003-05-05 | 2004-11-11 | Analytical Services And Materials Inc. | Erosion-resistant silicone coatings |
RU2006100647A (en) | 2003-06-17 | 2006-08-10 | Хенкель Кгаа (De) | Suppression of Vegetative Propagation of Fungi by Eugenol and / or Its Derivatives |
DE10327137A1 (en) | 2003-06-17 | 2005-01-05 | Henkel Kgaa | Inhibition of asexual propagation of fungi |
US7033673B2 (en) * | 2003-07-25 | 2006-04-25 | Analytical Services & Materials, Inc. | Erosion-resistant silicone coatings for protection of fluid-handling parts |
DE10358534A1 (en) | 2003-12-13 | 2005-07-14 | Henkel Kgaa | Adhesion inhibition of microorganisms by nonionic surfactants |
DE102004038104A1 (en) * | 2004-08-05 | 2006-02-23 | Henkel Kgaa | Use of ortho-phenylphenol and / or its derivatives for inhibiting the asexual propagation of fungi |
DE102004056362A1 (en) | 2004-11-22 | 2006-06-01 | Henkel Kgaa | Mold-resistant building materials |
DE102007030406A1 (en) | 2007-06-29 | 2009-01-08 | Henkel Ag & Co. Kgaa | Use of an algae extract for the temporary or permanent dressing of surfaces, reducing adhesion of biological material, preferably microorganisms or proteins, on surfaces and in detergents, cleaning agents and hand-washing agent |
DE102007034726A1 (en) | 2007-07-23 | 2009-01-29 | Henkel Ag & Co. Kgaa | Removal of by-products from crosslinkable preparations |
DE102007058343A1 (en) | 2007-12-03 | 2009-06-04 | Henkel Ag & Co. Kgaa | Reduction of the adhesion of dirt, dust and biological material by polyesteramides |
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US20130032262A1 (en) | 2011-08-02 | 2013-02-07 | Bormann Rene Louis | Tire with foamed noise damper |
KR102130348B1 (en) | 2011-11-10 | 2020-07-06 | 모멘티브 퍼포먼스 머티리얼즈 인크. | Moisture curable organopolysiloxane composition |
JP6297498B2 (en) | 2011-12-15 | 2018-03-20 | モーメンティブ・パフォーマンス・マテリアルズ・インク | Moisture curable organopolysiloxane composition |
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JP2015504946A (en) | 2011-12-29 | 2015-02-16 | モーメンティブ・パフォーマンス・マテリアルズ・インク | Moisture curable organopolysiloxane composition |
CN104640897B (en) * | 2012-09-25 | 2018-02-23 | 科思创德国股份有限公司 | Polyisocyanate polyaddition products |
US8888939B2 (en) | 2012-10-31 | 2014-11-18 | The Goodyear Tire & Rubber Company | Method of applying an annular strip to a tire |
TW201434882A (en) | 2013-03-13 | 2014-09-16 | Momentive Performance Mat Inc | Moisture curable organopolysiloxane compositions |
CN105358606B (en) | 2013-05-10 | 2018-02-16 | 莫门蒂夫性能材料股份有限公司 | The organopolysiloxane composition of nonmetal catalyzed room temperature moisture-curable |
US10241262B2 (en) * | 2015-10-14 | 2019-03-26 | Sumitomo Electric Industries, Ltd. | Optical fiber |
KR101893260B1 (en) | 2016-10-24 | 2018-10-04 | 한국타이어 주식회사 | Cavity noise reduction tire and manufacturing method thereof |
CN110997783A (en) | 2017-07-31 | 2020-04-10 | 美国陶氏有机硅公司 | Moisture curable compositions |
US11655404B2 (en) | 2019-12-23 | 2023-05-23 | Dow Silicones Corporation | Sealant composition |
CN112759609B (en) * | 2020-12-30 | 2022-07-01 | 硅宝(深圳)研发中心有限公司 | Double-component dehydrogenation type bonding heat-conducting potting adhesive and catalyst and preparation method thereof |
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-
1995
- 1995-09-13 DE DE19549425A patent/DE19549425A1/en not_active Withdrawn
-
1996
- 1996-09-02 AU AU69861/96A patent/AU711271B2/en not_active Ceased
- 1996-09-02 CA CA002231586A patent/CA2231586C/en not_active Expired - Fee Related
- 1996-09-02 CN CNB961979429A patent/CN1146582C/en not_active Expired - Lifetime
- 1996-09-02 JP JP51161297A patent/JP4157162B2/en not_active Expired - Fee Related
- 1996-09-02 WO PCT/EP1996/003838 patent/WO1997010271A1/en active IP Right Grant
- 1996-09-02 HU HU9901167A patent/HU224309B1/en not_active IP Right Cessation
- 1996-09-02 AT AT96930996T patent/ATE224920T1/en active
- 1996-09-02 DE DE59609733T patent/DE59609733D1/en not_active Expired - Lifetime
- 1996-09-02 EP EP96930996A patent/EP0850254B1/en not_active Expired - Lifetime
- 1996-09-02 NZ NZ318387A patent/NZ318387A/en not_active IP Right Cessation
- 1996-09-02 PL PL96326271A patent/PL186608B1/en unknown
- 1996-09-02 CZ CZ1998780A patent/CZ289135B6/en not_active IP Right Cessation
- 1996-09-02 ES ES96930996T patent/ES2184888T3/en not_active Expired - Lifetime
- 1996-09-12 US US09/043,185 patent/US6162756A/en not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
---|---|
HUP9901167A2 (en) | 1999-07-28 |
WO1997010271A1 (en) | 1997-03-20 |
US6162756A (en) | 2000-12-19 |
ZA967686B (en) | 1997-03-26 |
ATE224920T1 (en) | 2002-10-15 |
DE19549425A1 (en) | 1997-03-20 |
AU6986196A (en) | 1997-04-01 |
CA2231586C (en) | 2008-11-18 |
EP0850254A1 (en) | 1998-07-01 |
ES2184888T3 (en) | 2003-04-16 |
AU711271B2 (en) | 1999-10-07 |
PL326271A1 (en) | 1998-08-31 |
CZ289135B6 (en) | 2001-11-14 |
JP4157162B2 (en) | 2008-09-24 |
EP0850254B1 (en) | 2002-09-25 |
HUP9901167A3 (en) | 1999-11-29 |
HU224309B1 (en) | 2005-07-28 |
NZ318387A (en) | 1999-10-28 |
CZ78098A3 (en) | 1998-06-17 |
CN1200738A (en) | 1998-12-02 |
JP2000500166A (en) | 2000-01-11 |
DE59609733D1 (en) | 2002-10-31 |
PL186608B1 (en) | 2004-01-30 |
CA2231586A1 (en) | 1997-03-20 |
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